Polyphosphazine-based polymer materials

ABSTRACT

Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, β-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

CONTRACTUAL ORIGIN OF THE INVENTION

This invention was made with government support under Contract No.DE-AC07-05ID14517 awarded by the United States Department of Energy. Thegovernment has certain rights in this invention.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to methods and systems forremoving contaminant matter from natural and man-made porous materialsincluding, for example, cement, asphalt, tile, granite, marble, andother stone materials. The present invention also relates to polymermaterials that may be used in conjunction with such methods and systemsto remove contaminant matter from such materials.

2. State of the Art

Natural and man-made porous materials and structures employing suchmaterials may become contaminated with contaminant matter, such asradionuclides of uranium, plutonium, americium, californium, radium,iridium, cesium, strontium, and cobalt (as well as other fissionproducts of such radionuclides), due to radioactive waste disposal andstorage activities, unintentional leakage of radioactive waste, andfallout from atmospheric releases of radioactive material. For example,cement or asphalt roadways may be contaminated with radionuclides due tounintentional spills that occur during transportation of radioactivewaste material from a waste generation site to a waste storage site. Asanother example, surfaces of buildings, monuments, bridges or otherman-made structures that are formed from or are surfaced with porousmaterials, such as brick, cement, granite, marble, and other stonematerials, could be contaminated with radionuclides upon the detonationof a “dirty” bomb (a bomb that includes radioactive material) such asmight be detonated in an urban setting.

In events such as those described above, the contaminated structures andexposed surfaces of materials of such structures may need to bedecontaminated before persons are allowed within the vicinity of thecontaminated area and prior to resuming use of contaminated structuresand proximity to surfaces thereof. When contaminated structures includeporous materials (such as, for example, cement, asphalt, granite,marble, and other stone materials), at least some of the contaminantradionuclides may be deposited within pores, cracks, vugs and/or voidsthat extend into the porous materials from the exterior surfacesthereof. Contaminant radionuclides deposited within such pores, cracks,and/or voids may be relatively difficult to remove from the porousmaterial, thereby complicating the decontamination process for suchstructures.

Furthermore, when contaminant radionuclides are deposited on a structurethat includes a porous material, the radionuclides may become moretightly bound to the porous material with the passage of time, as theradionuclides migrate deeper within the pores, cracks, vugs and/or voidsof the porous material and form surface complexes with the substratematerials surrounding such pores, cracks, and/or voids. Therefore, itmay be necessary or desirable to remove radionuclides from contaminatedstructures and materials as soon as possible after a contaminatingevent. However, access to contaminated areas by decontaminationpersonnel may be delayed for a period of time after such a contaminatingevent. For example, access to contaminated areas by decontaminationpersonnel may be delayed until after emergency response personnel haveevacuated and secured the contaminated area, and identified the natureand extent of the contamination. Such delays of access to contaminatedareas by decontamination personnel may exacerbate the problem associatedwith the increasing difficulty of removing radionuclides from porousmaterials and structures with the passage of time.

One method for removing radionuclides from porous materials is describedin U.S. Pat. No. 5,421,906 to Borah. The method involves applying aprecleaning aqueous fluid to a contaminated surface, rinsing theprecleaning fluid from the surface with water or a solution of water andsodium citrate, applying an aqueous extraction fluid to the contaminatedsurface, and washing the extraction fluid from the surface. Theprecleaning aqueous fluid comprises from about 4 to about 10 wt. %sulfamic acid, from about 5 to about 10 wt. % hydrofluoric ammoniumbifluoride, from about 2 to about 4 wt. % hydrochloric acid, about 1 toabout 4 wt. % surfactant, about 6 to about 12 wt. % sodium citrate,about 2 to about 5 wt. % oxalic acid, about 10 to about 20 wt. %triethanolamine; and, optionally, about 1 to about 2 wt. % d-limonine.The aqueous extraction fluid comprises about 5 to about 8 wt. %surfactant, about 4 to about 8 wt. % of an emulsifier containingquaternary amines, isopropyl alcohol and glycerine, about 15 to about 20wt. % ethylene diamine tetracetic acid, about 5 to about 10 wt. %ethylene glycol monobutyl ether, about 4 to about 8 wt. % of a chemicalpH buffer agent, about 4 to about 8 wt. % triethanolamine, and about 4to about 10 wt. % of a composition selected from the group consisting ofethylene-bis(oxyethylenenitrilo)-tetracetic acid, 1,2diamino-cyclohexane-tetracetic acid, hydroxyethylene diamine tetraceticacid, nitrilotriacetic acid and sodium gluconate.

Another method for removing radionuclides from porous materials isdescribed in U.S. Pat. No. 5,763,734 to Nachtman et al. The methodinvolves applying polyurea elastomers, other isocyanate plural componentsystems, polyurethanes, polyamides, latex, or mixtures thereof, at atemperature of at least about 100° F., to a contaminated substrate, andthen removing the applied material to remove contaminants from thesubstrate.

BRIEF SUMMARY OF THE INVENTION

In one embodiment, the present invention includes apolyphosphazine-based polymer material that may be used to decontaminatea contaminated structure that includes a porous material. Thepolyphosphazine-based polymer material includes a plurality ofpolyphosphazine molecular segments. The polyphosphazine molecularsegments have side groups, which may include functional groups having achemical structure represented by at least one of the following chemicalfunctional groups:

wherein R₁ represents a phosphorous atom of a polyphosphazine backboneor a plurality of atoms providing a covalently bonded link to aphosphorous atom of a polyphosphazine backbone, and wherein R₂ comprisesadditional chemical structure. The polymer material may also be termed a“capture material” herein, although suitable capture materials are notso limited.

In another embodiment, the present invention includes a method ofremoving contaminant matter from a porous material. The method includesapplying a polymer material (such term including polymer materialprecursors) to a surface of a porous material comprising contaminantmatter in at least one pore thereof, irradiating the surface of theporous material with electromagnetic radiation either before or afterthe polymer material is applied, and removing at least a portion of thepolymer material in a cured state and having contaminant matterphysically, chemically or atomically bound thereto from the surface ofthe porous material. Irradiating the surface of the porous material maycause redistribution of the contaminant matter to enhance removalthereof by the polymer material. A reagent may, optionally, be appliedto the surface of the porous material prior to irradiation to enhancethe desired redistribution of the contaminant matter.

In yet another embodiment, the present invention includes a system fordecontaminating a contaminated structure comprising porous material. Thesystem includes at least one radiation device configured to emitelectromagnetic radiation toward a surface of a contaminated structure,and at least one spray device configured to apply a capture materialonto the surface of the contaminated structure. Such capture materialsmay include polymer materials or small molecules that are capable ofbinding to a radionuclide. Capture materials may bind to a radionuclideby, for example, forming a chemical complex therewith. The chemicalcomplex formed between the capture material and the radionuclide mayfacilitate removal of the radionuclide from a contaminated structure.

BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims particularly pointing outand distinctly claiming that which is regarded as the present invention,various features and advantages of this invention may be more readilyascertained from the following description of the invention when read inconjunction with the accompanying drawings, in which:

FIG. 1 is a flow chart illustrating an example of a method that embodiesteachings of the present invention and that may be used to removecontaminant matter from a porous material;

FIGS. 2A-2F illustrate an example of various acts in the processrepresented by the flow chart shown in FIG. 1;

FIG. 3 is a flow chart illustrating another example of a method thatembodies teachings of the present invention and that may be used toremove contaminant matter from a porous material;

FIGS. 4A-4F illustrate an example of various acts in the processrepresented by the flow chart shown in FIG. 3;

FIGS. 5A-5D illustrate an example of a method that may be used todetermine the adhesion force of a material with respect to a particularporous material to be decontaminated;

FIG. 6 is yet another flow chart illustrating additional methods thatembody teachings of the present invention and that may be used to removecontaminant matter from a porous material;

FIG. 7 is a schematic diagram of a decontamination system that embodiesteachings of the present invention; and

FIG. 8 illustrates a robotic vehicle on which a decontamination systemthat embodies teachings of the present invention is mounted.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the term “porous material” means any material thatincludes one or more of pores, cracks, fissures, vugs and voidsextending into the material from external surfaces thereof. Further, theterm “pore” includes and encompasses cracks, fissures, vugs and voids.Porous materials may include, for example, concrete, alumino-silicates,metals, minerals, polymers, ceramics, composites, asphalt, brick,mortar, and all types of architectural and structural stone, so long assuch materials include one or more of pores, cracks, fissures, or voidsextending into the material from external surfaces thereof.

An example of a method that embodies teachings of the present inventionand that may be used to remove contaminant matter from a porous materialwill be described with reference to FIG. 1 and FIGS. 2A-2F. FIG. 1 is aflow chart that illustrates acts of the method. As shown therein, themethod involves irradiating a contaminated structure withelectromagnetic radiation to cause redistribution of contaminant matter,applying a polymer material to the structure that is configured to bindto the contaminant matter, and removing the polymer material togetherwith contaminant matter bound thereto from the structure. This processwill be described in further detail with reference to FIGS. 2A-2F.

FIG. 2A is a partial cross-sectional view of a structure 10 thatincludes a porous material 12. By way of example and not limitation, thestructure 10 may include masonry of a building, a sidewalk, a road,monument, or other urban structure, and the porous material 12 mayinclude cement, asphalt, tile, granite, marble, or any other porousmaterial. A fissure or crack 14 is shown, which extends into the porousmaterial 12 from a surface 16 of the structure 10. It is understood thatthe structure 10 may include pores or voids of any shape orconfiguration that extend into the porous material 12 from the surface16 in addition to, or instead of, cracks 14.

Atoms, molecules, or larger particles of contaminant matter 20 may bedisposed on the surface 16 of the structure 10 and within the crack 14extending into the porous material 12, as shown in FIG. 2A. By way ofexample and not limitation, the contaminant matter 20 may include ametal (including Group I metals, Group II metals, transition metals,lanthanide series metals, and actinide series metals). Furthermore, thecontaminant matter 20 may include a metal that is a radionuclide suchas, for example, uranium, plutonium, americium, californium, radium,iridium, cesium, strontium, and cobalt (as well as fission products ofsuch radionuclides).

Referring to FIG. 2B, to decontaminate the structure 10, the structure10 may be irradiated with electromagnetic radiation 24 to causeredistribution of the contaminant matter 20. In other words, irradiationof the structure 10 may cause at least some of the contaminant matter 20within the crack 14 to move in a direction generally toward the surface16 of the structure 10, as shown in FIG. 2C. Furthermore, at least somecontaminant matter 20 initially within the crack 14 may be transportedto and deposited on the surface 16 of the structure 10 uponredistribution.

The irradiation process may be nondestructive. In other words,irradiation of the structure 10 with electromagnetic radiation 24 maynot cause significant ablation of the porous material 12. Moreparticularly, the power of the electromagnetic radiation 24 impinging onthe structure 10 may be below an ablation power threshold of the porousmaterial 12. The ablation power threshold of the porous material 12 maybe defined as the power per unit area applied to a surface, above whichapplied power per unit area significant (e.g., perceptible) ablation ofthe material 12 defining the surface occurs when the electromagneticradiation 24 impinges on the material 12. Furthermore, the power of theelectromagnetic radiation 24 may be selectively tailored to provide aselected level of redistribution of the contaminant material 20 whileproviding a maximum acceptable level of ablation of the porous material12. As an example, the power of the electromagnetic radiation 24 may beadjusted to a level just below an ablation power threshold of the porousmaterial 12.

By way of example and not limitation, the surface 16 of the structure 10may be irradiated with electromagnetic radiation 24 having a wavelengthor wavelengths in a range extending from about 200 nanometers to about25 centimeters. Furthermore, the structure 10 may be irradiated with abeam of substantially coherent electromagnetic radiation 24, such asthat emitted by laser or maser devices. For example, a laser deviceconfigured to emit a beam of substantially coherent electromagneticradiation 24 having a wavelength in a range extending from about 200nanometers to about 2500 nanometers may be used to irradiate the surface16 of the structure 10. As another example, a carbon dioxide laserconfigured to emit a beam of substantially coherent electromagneticradiation 24 having a wavelength in a range extending from about 9microns to about 11 microns may be used to irradiate the surface 16 ofthe structure 10. Furthermore, laser devices emitting more than onewavelength of electromagnetic radiation may be used in combination toemit electromagnetic radiation 24 and provide a selected multi-modaldistribution of wavelengths in the electromagnetic radiation 24 incidenton the structure 10. For example, a first laser device may be configuredto emit electromagnetic radiation 24 having a wavelength of about 337nanometers, and a second laser device may be configured to emitelectromagnetic radiation 24 having a wavelength of about 1064nanometers. The electromagnetic radiation 24 emitted by the first laserdevice and the electromagnetic radiation 24 emitted by the second laserdevice may be focused so as to be coincident on the surface 16 of thestructure 10. The use of a selected multi-modal distribution ofwavelengths in the electromagnetic radiation 24 may mitigate damage tothe structure 10 while enhancing redistribution of the contaminantmatter 20.

As yet another example, a flash lamp-type device configured to emitelectromagnetic radiation 24 having wavelengths in the ultravioletand/or visible regions of the electromagnetic spectrum may be used toirradiate large areas of the surface 16 of the structure 10. Optionally,optical components (not shown) such as lenses, prisms, mirrors, andfilters may be used in conjunction with a radiation-emitting device tocollimate, focus, and/or filter the electromagnetic radiation 24 emittedthereby as necessary or desired.

Only a single crack 14 is illustrated in FIGS. 2A-2D for simplicity ofillustration. The surface 16 of the structure 10, however, may berelatively large and may include innumerable cracks 14 and/or pores. Asa result, a beam of electromagnetic radiation 24 on the surface 16 ofthe structure 10 may be systematically scanned, such as (by way ofexample only) by use of raster scanning techniques, over the surface 16of the structure 10 to cover larger areas on the surface 16 (e.g., areasgreater than about one-hundred times the surface area of the spot sizeof the beam of incident electromagnetic radiation 24).

As previously discussed, irradiation of the structure 10 (as shown inFIG. 2B) may cause at least some of the contaminant matter 20 within thecrack 14 to be redistributed in a direction generally toward a surface16 of the structure 10 (as shown in FIG. 2C). The mechanism by which theelectromagnetic radiation 24 causes redistribution of the contaminantmatter 24 is not fully understood, although it is believed thatphotophysical mechanisms (i.e., acoustic and thermal vibrations) and/orphotochemical mechanisms (i.e., electronic transitions) may at leastpartly contribute to the redistribution of the contaminant matter 20.

Referring to FIG. 2D, a capture material 28 may be applied to thesurface 16 of the structure 10 after the structure 10 has beenirradiated with electromagnetic radiation 24, as previously described.The capture material 28 may be any material that is capable of binding(chemically or physically) to the contaminant material 20, and that maybe subsequently removed from the structure 10. By way of example and notlimitation, the capture material 28 may include a polymer material.

As an example, the capture material 28 may include a thermoplasticpolymer material such as, for example, polyethylene-based materials,polyurethane-based materials, polypropylene-based materials,polyester-based materials, polyamide-based materials, acrylic-basedmaterials, polyvinylacetyl-based materials (such as, for example,polyvinylbutyral-based materials), polyvinylacetate-based materials,polyisoprene-based materials, styrenebutadiene-based materials, andlatex-based materials. In such an embodiment, the capture material 28may be applied to the surface 16 of the structure 10 by, for example,heating the capture material 28 to a temperature above a glasstransition temperature of the capture material 28 to substantiallyliquefy the capture material 28, spraying droplets of the substantiallyliquefied capture material 28 onto the surface 16 of the structure 10,and allowing the capture material 28 as applied to cool and solidify, toform a substantially continuous layer of capture material 28 extendingover at least a portion of the surface 16 of the structure 10.

As another example, the capture material 28 may include a thermosetpolymer material such as, for example, silicone-based materials orepoxy-based materials. In such an embodiment, the capture material 28may be applied to the surface 16 of the structure 10 by, for example,applying substantially liquid uncured polymer material or polymerprecursor materials to the surface 16 of the structure 10, andsubsequently curing the uncured polymer material or polymer precursormaterials to form the capture material 28. By way of example and notlimitation, the polymer materials or polymer precursor materials may becured by applying energy in the form of heat and/or electromagneticradiation to the precursor materials. Alternatively, the polymerprecursor materials may be cured by mixing a chemical reagent with thepolymer precursor materials immediately prior to application of thepolymer precursor materials to the surface 16 of the structure 10, or byapplying the reagent to the polymer precursor materials afterapplication to the surface 16.

If the substantially liquid uncured polymer material or polymerprecursor materials may be cured by irradiating the polymer precursormaterials with electromagnetic radiation 24, the polymer precursormaterials may be cured while substantially simultaneously causingredistribution of the contaminant matter 20 by irradiating the structure10 with electromagnetic radiation 24 as discussed previously in relationto FIG. 2B.

Referring to FIG. 2E, the capture material 28, together with thecontaminant matter 20 captured thereby, may be removed from the surface16 of the structure 10. By way of example and not limitation, thecapture material 28 may be removed from the surface 16 of the structure10 by peeling the capture material 28 off from the structure 10, asshown in FIG. 2E. In additional embodiments, the capture material 28 maybe scraped, ground, or polished off from the surface 16 of the structure10.

After the capture material 28 and the contaminant matter 20 have beenremoved from the surface 16 of the structure 10, the structure 10 may besubstantially free of contaminant matter 20, as shown in FIG. 2F. If thestructure 10 is not substantially free of contaminant matter 20 after asingle decontamination treatment, the process may be repeated asnecessary or desired until the amount of contaminant matter 20 remainingon the surface 16 of the structure 10 reaches a selected acceptablelevel.

Another illustrative method that embodies teachings of the presentinvention and that can be used to remove contaminant matter from aporous material will be described with reference to FIG. 3 and FIGS.4A-4F. FIG. 3 is a flow chart broadly illustrating the acts of themethod. As shown therein, the method involves applying a transparentpolymer material that is configured to bind to a contaminant matter to astructure, irradiating the structure through the polymer material withelectromagnetic radiation to cause redistribution of contaminant matter,and removing the polymer material together with contaminant matter boundthereto from the structure. This process will be described in furtherdetail with reference to FIGS. 4A-4F. As used herein, the term“transparent” means at least partially transmissive of the intendedwavelength or wavelengths of electromagnetic radiation to besubsequently applied to the structure, and is not limited to materialstransparent to such radiation lying within the range visible to humans.

FIG. 4A is identical to the FIG. 2A previously described herein, and isa partial cross-sectional view of the structure 10, which includes aporous material 12. A crack 14 is illustrated that extends into theporous material 12 from the surface 16. Contaminant matter 20 isdisposed on the surface 16 of the structure 10 and within the crack 14.A transparent capture material 28 may be applied to the surface 16 ofthe structure 10, as shown in FIG. 4B, after which the structure 10 maybe irradiated with electromagnetic radiation 24 through the capturematerial 28, as shown in FIG. 4C. In this method, the capture material28 is applied to the structure 10 prior to irradiating the structure 10with electromagnetic radiation 24, in contrast to the method previouslydescribed herein in relation to FIGS. 2A-2F.

Irradiation of the structure 10, as shown in FIG. 4C, may cause at leastsome of the contaminant matter 20 within the crack 14 to beredistributed in a direction generally toward the surface 16 of thestructure 10, as shown in FIG. 4D. The capture material 28 may bind tothe contaminant matter 20. Referring to FIG. 4E, the capture material28, together with the contaminant matter 20 captured thereby, may beremoved from the surface 16 of the structure 10 as previously describedherein to provide a structure 10 that is substantially free ofcontaminant matter 20, as shown in FIG. 4F. If the structure 10 is notsubstantially free of contaminant matter 20, the process may be repeatedas necessary or desired until the amount of contaminant matter 20remaining on the surface 16 of the structure 10 reaches a selectedacceptable level.

In this method, a layer of the capture material 28 having a thickness ofless than about one centimeter may be at least partially transparent toone or more wavelengths of electromagnetic radiation 24 incident on thestructure 10.

By way of example and not limitation, the capture material 28 mayinclude a polyphosphazine-based polymer material. For example, thepolyphosphazine-based material may include a polymer or copolymermaterial including polyphosphazine molecular segments having a chemicalstructure generally represented as:

where P represents phosphorous, N represents nitrogen, and A representsa side chain group or chemical structure comprising an atom or aplurality of covalently bonded atoms. In some embodiments, the value ofn may be between about 500 and about 15,000. More particularly, thevalue of n may be between about 6,000 and about 10,000. The alternatingphosphorous-nitrogen chain may be referred to as the polyphosphazinebackbone.

By way of example and not limitation, the side chain groups A mayinclude, for example, Cl, F, Br, OC_(n)H_(2n+1) (where n is an integerbetween 1 and about 10), OCH₂CF₃, NHCH₃. Furthermore, one or more of thespecies of side chain groups A may provide a cross-link to anotherpolyphosphazine backbone.

Moreover, one or more of the side chain groups A may include afunctional group selected to perform one or more of the followingfunctions: bind to the contaminant matter 20, bind to the porousmaterial 12, and impart selected physical properties (such as, forexample, elasticity) to the capture material 28 to facilitate removal ofthe capture material 28 from the porous material 12. Such functionalgroups may include, for example, primary amines, secondary amines,tertiary amines, iminos, oximes, carboxylates, sulfonates, β-diketones,phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates,phosphine oxides, monothio phosphinic acids, and dithio phosphinicacids. In terms of chemical structures, such functional groups may havechemical structures selected from the following group:

In the above-illustrated functional groups, the R₁ groups may be aphosphorous atom of a polyphosphazine backbone or one or more atomsproviding a covalently bonded link to a phosphorous atom of apolyphosphazine backbone. The R₂ groups may include any additionalchemical structure, and may include, for example, an alkyl group. Inadditional embodiments, some R₂ groups may also include one or moreatoms providing a covalently bonded link to a phosphorous atom of apolyphosphazine backbone. In such configurations, the functional groupsmay comprise portions of chemical structures providing cross-linksbetween different polyphosphazine backbones.

If the functional groups are configured to bind to the porous material12, the functional groups may be configured to promote hydrogen bondingbetween the capture material 28 and the porous material 12. For example,the functional groups may include hydrogen atoms and/or chlorine,fluorine, or bromine atoms to promote hydrogen bonding between thecapture material 28 and the porous material 12.

Various methods known in the art may be used to synthesizepolyphosphazine materials. By way of example and not limitation, themacromolecular substitution method may be used to synthesize suchpolyphosphazine materials. The macromolecular substitution methodinvolves forming hexachlorocyclotriphosphazene from phosphorouspentachloride and ammonium chloride, heating thehexachlorocyclotriphosphazene to a temperature of greater than about250° C. to form poly(dichlorophosphazene), and replacing the chlorineatoms of the poly(dichlorophosphazene) with the organic ororganometallic side groups R. In additional methods,poly(difluorophosphazene) may be used instead of, or in addition topoly(dichlorophosphazene) when forming polyphosphazine materials for useaccording to the present invention.

The capture material 28 may be selectively tailored to exhibit one ormore desired physical properties. For example, the capture material 28may be configured to exhibit between about 70 and about 1,500 percentelongation at failure of when tested in accordance with ASTM (AmericanSociety for Testing and Materials) standard D638-03, entitled StandardTest Method for Tensile Properties of Plastics. As another example, thecapture material 28 may be selectively tailored such to exhibit amaximum tensile strength at break in a range extending from about 1.0megapascals (MPa) to about 60.0 megapascals (MPa) when tested inaccordance with ASTM (American Society for Testing and Materials)standard D638-03, entitled Standard Test Method for Tensile Propertiesof Plastics. Other techniques for determining the maximum tensilestrength of a material using commercially available material testingmachines are also known in the art. As yet another example, the capturematerial 28 may be selectively tailored to exhibit a pull index, withrespect to a particular porous material 12 to be treated, in a rangeextending from about 40 cm⁻¹ to about 200 cm⁻¹. More particularly, thecapture material 28 may be selectively tailored to exhibit a pull index,with respect to a particular porous material 12 to be treated, in arange extending from about 60 cm⁻¹ to about 100 cm⁻¹. The pull index ofthe capture material 28 may be defined as the maximum tensile strengthat break of the capture material 28 divided by the adhesion force of thecapture material 28 with respect to the particular porous material 12 tobe treated.

An example of a method for determining the adhesion force of the capturematerial 28 with respect to the particular porous material 12 to betreated, which is performed using a commercially available materialtesting machine (such as those sold by Instron of Norwood, Mass.), willnow be described with reference to FIGS. 5A-5D. FIG. 5A is a top planview of a sample or block 40 of the particular porous material 12 to betreated, which is used to determine the adhesion force of the capturematerial 28 with respect to the particular porous material 12. FIG. 5Bis a side view of the block 40. As seen in FIGS. 5A and 5B, the block 40has a substantially planar test surface 41. The test surface 41 issubstantially rectangular, having a length L and a width W. The length Lis 7.62 cm (3 in.), and the width W is 2.54 cm (1 in.). A piece of meshmaterial 44 comprising, for example, nylon, is temporarily adhered(using a low-strength adhesive material) to the test surface 41 at anend of the block 40, such that about half of the piece of mesh material44 extends laterally beyond a side surface 42 of the block 40. The pieceof mesh material 44 is substantially square, having side lengths ofabout 2.54 cm (1 in.).

Referring to FIG. 5C, a capture material 28 then may be applied to thetest surface 41 of the block 40, including over the portion of the pieceof mesh material 44 that overlies the test surface 41, such that thecapture material 28 penetrates into the mesh material 44. Referring toFIG. 5D, one set of grips or a clamp of the testing machine may besecured to the block 40, and another set of grips or a second clamp ofthe testing machine may be secured to the portion of the piece of meshmaterial 44 that extends laterally beyond the side surface 42 of theblock 40. The testing machine may be caused to pull the piece of meshmaterial 44 (and the capture material 28 attached thereto) in adirection substantially perpendicular to the planar test surface 41, asindicated by the directional arrow F in FIG. 5D, at a rate of about 5.0cm per minute while measuring the force acting on the load cell of thetesting machine. The stress-strain curve may be generated and plottedfrom the collected data. The adhesion force of the capture material 28with respect to the particular porous material 12 (FIG. 2A) to betreated may be defined as the average of the force in the “plateau”region of the resulting stress-strain curve (i.e., the region ofgenerally constant force relative to other regions of the stress straincurve (such as the end portions of the stress-strain curve)), divided bythe width W of block 40 (FIG. 5A) (assuming that the capture material 28extends over the entire test surface 41 of the block 40). If necessaryor desired, this process may be repeated a number of times (up to about30) using substantially identical samples, so as to determine theadhesion force of the capture material 28 with respect to the particularporous material 12 with a satisfactory statistical confidence level.

FIG. 6 is another flow chart generally illustrating additional methodsfor removing contaminant matter 20 from a porous material 12 that embodyteachings of the present invention. In FIG. 6, the process illustratedin the flow chart of FIG. 1 is contained within the dashed line 34, andthe process illustrated in the flow chart of FIG. 3 is contained withinthe dashed line 36.

As shown in FIG. 6, a reagent optionally may be applied to a structure10 prior to performing the method previously described in relation toFIGS. 2A-2F or the method previously described in relation to FIGS.4A-4F. The reagent may facilitate redistribution of the contaminantmatter 20 by forming complexes with the contaminant matter 20 that aremore susceptible to redistribution relative to the contaminant matter 20alone. By way of example and not limitation, such a reagent may includeone or more of 1-methoxy-2-(2-methoxyethoxy)ethane(diglyme), sodiumborohydride, and β-diketones (such as, for examplepentane-2,4-dione(acetylacetone), acetonylacetone,trifluoroacetylacetone, hexafluoroacetylacetone,thienoyltrifluoroacetylacetone, and2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione and2,2,6,6-tetramethylheptane-3,5-dione).

In some instances, after the capture material 28 and the contaminantmatter 20 have been removed from the surface 16 of the structure 10 aspreviously discussed herein, at least some contaminant matter 20 mayremain on the surface 16 and/or within the cracks 14 of the structure10. In such instances it may be necessary or desirable to repeat theprocesses previously described herein one or more times in order toensure that the surface 16 of the structure 10 is substantially free ofcontaminant matter 20, as shown in FIG. 2F and FIG. 4F.

As shown in FIG. 6, after performing the process previously described inrelation to FIGS. 2A-2F or the process previously described in relationto FIGS. 4A-4F, the amount of contaminant matter 20 remaining on thesurface 16 or in the cracks 14 of the porous material 12 optionally maybe estimated or determined. By way of example and not limitation, theamount of contaminant matter 20 remaining on the surface 16 or in thecracks 14 of the porous material 12 may be estimated or determined bydetecting contaminant matter 20 remaining on or in the porous material12. For example, chemical analysis techniques known in the art may beused to detect contaminant matter 20 remaining on or in the porousmaterial 12. In additional embodiments, the amount of contaminant matter20 bound to the capture material 28 may be detected after removing thecapture material 28 from the structure 10. The process described inrelation to FIGS. 2A-2F or the process previously described in relationto FIGS. 4A-4F may be repeated until the amount of contaminant matter 20detected on or in the porous material 12, or in the capture material 28removed from the structure 10, has been reduced to a selected level.

The methods for decontaminating a structure 10 previously describedherein may be at least partially carried out using a decontaminationsystem 50 schematically illustrated in FIG. 7, which embodies teachingsof the present invention. As seen in FIG. 7, the decontamination system50 may include at least one spray device 52 configured to apply capturematerial 28 to a surface 16 of a structure 10 that includes porousmaterial 12 (FIG. 2A). For example, the spray device 52 may beconfigured to spray a substantially liquid polymer capture material 28,or polymer precursor materials used to form a capture material 28, on asurface 16 of a structure 10. The spray device 52 may include acontainer (not shown) for holding substantially liquid polymer capturematerial 28, or precursor materials used to form capture material 28, apump (not shown) for pressurizing the liquid within the container, and aspray nozzle (not shown) configured to direct the liquid onto thesurface 16 of a structure 10. Optionally, the spray device 52 mayfurther include one or more heating elements configured to maintain theliquid at or above a selected temperature while the liquid is within thecontainer, the spray nozzle, and/or fluid supply lines or hosesextending therebetween.

The decontamination system 50 optionally may include an additional spraydevice 52 configured to apply a chemical reagent that facilitatesredistribution of contaminant matter 20 to a surface 16 of a structure10 (FIG. 2A) prior to applying a capture material 28 to the surface 16of the structure 10. In other embodiments, the decontamination system 50may include a single spray device 52 that is configured to selectivelyapply both a chemical reagent that facilitates redistribution ofcontaminant matter 20 and a capture material 28 to a surface 16 of astructure 10 (FIG. 2A).

The decontamination system 50 may further include at least one radiationdevice 54 configured to irradiate a surface 16 of a structure 10 thatincludes porous material 12 (FIG. 2A). By way of example and notlimitation, the radiation device 54 may include a laser deviceconfigured to emit a beam of substantially coherent electromagneticradiation 24 (FIG. 2B). In additional embodiments, the decontaminationsystem 50 may include a plurality of radiation devices 54, eachconfigured to emit a beam of substantially coherent electromagneticradiation 24 having a unique wavelength or wavelengths to provide aselected multi-modal distribution of electromagnetic radiation 24.

The decontamination system 50 may include at least one control device 56configured to selectively control the various other components of thedecontamination system 50, such as, for example, the spray device 52 andthe radiation device 54. The control device 56 may include, for example,at least one electronic signal processor device (not shown), at leastone memory device (not shown), and at least one input device (not shown)for receiving commands from a person operating the system 50, as well asfrom sensors indicating proximity to a contaminated surface or atemperature thereof, etc. By way of example and not limitation, thecontrol device 56 may include a computer device such as a personalcomputer (i.e., a desktop computer or a laptop computer), a programmablelogic controller, or an electronic control unit configured to receivecommands from another control device (not shown) disposed at a remotelocation via electrical wires extending therebetween or using anywireless technology known in the art (e.g., signals carried byelectromagnetic radiation). Remote operation of the decontaminationsystem 50 may be desirable in situations in which the nature of thecontaminant matter 20 renders local operation of the decontaminationsystem 50 unsafe for decontamination personnel. In such a configuration,the decontamination system 50 may further include a camera device (notshown) or other sensors, such term including global positioning system(GPS) sensors and associated transmitters configured to provide visualor other feedback regarding the location and orientation of thedecontamination system 50 to facilitate remote operation and controlthereof by decontamination personnel.

The decontamination system 50 may include a power device 58 configuredto supply electrical power as necessary or desired to the various othercomponents of the decontamination system 50, such as, for example, thespray device 52, the radiation device 54, and the control device 56. Byway of example and not limitation, the power device 58 may include oneor more batteries, an electrical generator, or a device configured toconnect to an existing power supply grid.

At least a portion of the decontamination system 50 may be mounted to avehicle 62 such as a truck, tractor, tractor trailer, all-terrainvehicle, remotely operated robotic device, etc., and the decontaminationsystem 50 optionally may include a drive assembly 60. The drive assembly60 may include a combustion engine or electrical motor configured todrive one or more wheels or a track assembly for moving the vehicle 62relative to the ground or other surface. If the drive assembly 60includes an electrical motor, electrical power may be supplied to theelectrical motor by the power device 58 or a different power devicededicated solely to the drive assembly 60.

By way of example and not limitation, the decontamination system 50 maybe mounted to a remotely operated robotic vehicle 62, such as thevehicle 62 shown in FIG. 8. The vehicle 62 may include a roboticplatform 64, such as that described in detail in U.S. Pat. No. 6,431,296to Won, the disclosure of which is incorporated herein in its entiretyby this reference. Briefly, the robotic platform 64 may include aprimary wheel and track system that includes a first set of tracks 66for propelling the robotic platform 64 along the ground or othersurface, and a second wheel and track system that includes a second setof tracks 68 to facilitate maneuvering of the robotic platform 64 overor relative to obstacles, such as steps and stairs. In additionalembodiments, the robotic platform 64 may include a plurality of wheelsconfigured to propel the robotic platform 64 relative to the ground,instead of the tracks 66 and tracks 68.

The robotic platform 64 may include a main body 70 (which may include aframe and/or a platform) on which a decontamination system 50 (FIG. 7)may be mounted. In other words, the spray device 52, radiation device54, control device 56, power device 58, and the drive assembly 60previously described herein with reference to FIG. 7 may be mounted on,or otherwise structurally coupled to, the main body 70 of the roboticplatform 64. The location and orientation of the spray device 52 andradiation device 54 may, of course, be dictated by the surfaces intendedto be decontaminated. For example, decontamination of horizontalsurfaces such as roadways may be effected by a spray device 52 andradiation device 54 suspended beneath robotic platform 64.

As shown in FIG. 8, a robotic arm 72 may be structurally coupled to therobotic platform 64. The robotic arm 72 may be configured to move in oneor more directions relative to the main body 70 of the robotic platform64. By way of example and not limitation, the robotic arm 72 may beconfigured to rotate about the vertical axis 76 relative to the mainbody 70 of the robotic platform 64 in the directions illustrated bydirectional arrow 77. The angle of inclination 78 of the robotic arm 72(i.e., the angle between the vertical axis 76 and a longitudinal axis(not shown) of the robotic arm 72) also may be selectively adjustable.Furthermore, the robotic arm 72 may be configured to selectively extendor retract in a linear direction 79 along a longitudinal axis of therobotic arm 72. In additional embodiments, the robotic arm 72 maycomprise an articulated robotic arm configured to selectively move inthree dimensions relative to the main body 70 of the robotic platform64.

Optionally, a generally laterally extending cross-bar 80 may be attachedto an end of the robotic arm 72, as shown in FIG. 8. In such aconfiguration, a spray unit 84 of the spray device 52 (FIG. 7) may bemounted on the cross-bar 80 and configured to selectively slide in thelateral direction thereon, as illustrated by the directional arrow 85.Supply lines or hoses 86 may be used to transport liquid for formingcapture material 28 (FIG. 2D) from a liquid holding tank 88 to aninjection nozzle or port 90 on the spray unit 84. In this configuration,spraying of capture material 28 onto the walls and/or roofs of buildingsor other structures may be facilitated.

At least a portion of the radiation device 54 (FIG. 7) also may bemounted on the robotic arm 72 to facilitate irradiating the walls and/orroofs of buildings or other structures with electromagnetic radiation24, as previously discussed herein. For example, fiber optic cables 94may be used to transport electromagnetic radiation 24 (FIG. 2B) emittedby a laser device 96 mounted to an additional port 98 on the spray unit84, from which the electromagnetic radiation 24 may be emitted towards asurface of a structure to be decontaminated. As shown in FIG. 8, thelaser device 96 may also be mounted on the main body 70 of the roboticplatform 64.

To decontaminate a structure 10 that includes a porous material 12, thevehicle 62 may be remotely controlled by an operator from a remotelocation. The robotic platform 64 may be driven to a location proximatethe contaminated structure 10, and the structure 10 may bedecontaminated using methods that embody teachings of the presentinvention, such as, for example, the methods illustrated in the flowcharts of FIG. 1, FIG. 3, and FIG. 6. For example, a capture material 28may be applied to a selected area on a surface 16 of the structure 10,as previously described in relation to FIG. 4B, using the nozzle or port90 on the spray unit 84, hoses 86, liquid holding tank 88, and a pump(not shown) for pressurizing the liquid in one or more of the spray unit84, hoses 86, and tank 88. By remote operation, the spray unit 84 may beselectively slid along the cross-bar 80, and the robotic arm 72 may beselectively maneuvered such that the selected area on the surface 16 ofthe structure 10 has been sufficiently coated with capture material 28.

The selected area on the surface 16 of the structure 10 then may beirradiated with electromagnetic radiation 24, as previously described inrelation to FIG. 4C, using the additional port 98 on the spray unit 84,fiber optic cables 94, and the laser device 96. Again, the spray unit 84may be selectively slid along the cross-bar 80, and the robotic arm 72may be selectively maneuvered, such that the selected area on thesurface 16 of the structure 10 has been sufficiently irradiated withelectromagnetic radiation 24, by remote operation.

After the structure 10 has been coated with capture material 28 andirradiated with electromagnetic radiation 24 to cause redistribution ofcontaminant matter 20, decontamination personnel may remove the capturematerial 28 together with contaminant matter 20 bound thereto using anyof the methods previously described herein. In some embodiments, thevehicle 62 may be equipped with means for removing the capture material28 from the structure 10. For example, at least one additional roboticarm (not shown) having a clamping or gripping member on an end thereofmay be mounted on the robotic platform 64. The additional robotic armmay be configured to clamp onto or grip capture material 28 after it hasbeen applied to a surface 16 of a structure 10, and to peel or tear thecapture material 28 off from the surface 16 of the structure 10.

In additional embodiments, it may not be necessary or desirable toremotely control and operate the vehicle 62, the vehicle 62 may beconfigured to be driven and controlled by an operator riding thereon orwithin a sealed operator compartment therein.

In additional embodiments, a decontamination system 50 (FIG. 7) may bemounted on an apparatus that is capable of decontaminating the walls andsurfaces of buildings or other structures that are too high to bereached using a robotic arm of a vehicle, such as the robotic arm 72 ofthe vehicle 62 shown in FIG. 8. For example, a decontamination system 50may be mounted on a frame or structure that can be suspended by cablesfrom the roof of a building, mounted on scaffolding secured adjacent abuilding, or otherwise positioned adjacent walls or other generallyvertical surfaces. Such an apparatus also may be remotely operated andconfigured to selectively “crawl” or move along the walls or othergenerally vertical surfaces of buildings or structures and used todecontaminate the buildings or structures using methods that embodyteachings of the present invention, such as those previously describedherein.

Although this invention has been described with reference to particularembodiments, the invention is not limited to these describedembodiments. Rather, the invention is limited only by the appendedclaims, which include within their scope all equivalent devices ormethods that operate according to the principles of the invention asdescribed.

1. A polyphosphazine-based polymer material comprising a plurality ofpolyphosphazine backbones having a chemical structure represented as

where N is nitrogen, P is phosphorous, n is an integer between about 500and about 15,000, and A is a chemical structure comprising at least onefunctional group having a chemical structure represented by at least oneof

wherein R₁ comprises a phosphorous atom of a polyphosphazine backbone ora plurality of atoms providing a covalently bonded link to a phosphorousatom of a polyphosphazine backbone, and wherein R₂ comprises additionalchemical structure.
 2. The polyphospazine-based polymer material ofclaim 1, wherein n is an integer between about 6,000 and about 10,000.3. The polyphospazine-based polymer material of claim 1, wherein a filmof the polyphosphazine-based polymer material having a thickness of lessthan about one centimeter is substantially transparent to at least onewavelength of radiation in a range extending from about 200 nanometersto about 25 centimeters.
 4. The polyphosphazine-based polymer materialof claim 1, wherein the polyphosphazine-based polymer material isconfigured to exhibit an average pull index with respect to a materialto which it is applied in a range extending from about 40 cm⁻¹ to about200 cm⁻¹.
 5. The polyphosphazine-based polymer material of claim 4,wherein the polyphosphazine-based polymer material is configured toexhibit an average pull index with respect to a material to which it isapplied in a range extending from about 60 cm⁻¹ to about 100 cm⁻¹. 6.The polyphosphazine-based polymer of claim 1, wherein thepolyphosphazine-based polymer material exhibits a maximum tensilestrength in a range extending from about 1 MPa to about 60 MPa.
 7. Thepolyphosphazine-based polymer material of claim 1, wherein R₂ comprisesan alkyl group.
 8. The polyphosphazine-based polymer material of claim1, wherein R₂ comprises a phosphorous atom of a polyphosphazine backboneor a plurality of atoms providing a covalently bonded link to aphosphorous atom of a polyphosphazine backbone.
 9. Thepolyphosphazine-based polymer material of claim 1, wherein thepolyphosphazine-based polymer material comprises a copolymer material.